Kp Expressions - Deduction
- We have seen previously that equilibrium reactions can be quantified by reference to an equilibrium expression and equilibrium constant
- The equilibrium expression links the equilibrium constant, Kc, to the concentrations of reactants and products at equilibrium taking the stoichiometry of the equation into account
- So, for a given reaction:
aA + bB ⇌ cC + dD
Kc is defined as follows:
Equilibrium expression linking the equilibrium concentration of reactants and products at equilibrium
- Solids are ignored in equilibrium expressions
- The Kc of a reaction is constant and only changes if the temperature of the reaction changes
Homogeneous reactions
- In the generic example above, if all the substances are gases, we can show the equation with that state symbol
aA (g) + bB (g) ⇌ cC (g) + dD (g)
- We can write a different equilibrium expression in terms of the partial pressure of the gases
- This equilibrium constant is called Kp and is defined as follows
Equilibrium expression linking the partial pressures of reactants and products at equilibrium
Heterogeneous reactions
- For heterogenous reactions, solids and liquids are ignored in Kp equilibrium expressions
- The Kp of a reaction is constant and only changes if the temperature of the reaction changes
Worked Example
Write a Kp expression for the following equilibria and deduce the units of Kp :
- N2 (g) + 3H2 (g) ⇌ 2NH3 (g)
- CaCO3 (s) ⇌ CaO (s) + CO2 (g)
Answer 1
Answer 2
Kp = pCO2(g)
Kp Expressions - Calculations
Calculations involving Kp
- In the equilibrium expression, the p represents the partial pressure of the reactants and products in Pa
- The units of Kp therefore depend on the form of the equilibrium expression
Worked Example
Calculating Kp of a gaseous reaction
Sulfur dioxide and oxygen react according to the following equation:
2SO2 (g) + O2 (g) ⇌ 2SO3 (g)
The equilibrium partial pressures at constant temperature are:
- SO2 =1.0 x 106 Pa
- O2 = 7.0 x 106 Pa
- SO3 = 8.0 x 106 Pa
Calculate the value of Kp for this reaction.
Answer
-
- Step 1: Write the equilibrium constant for the reaction in terms of partial pressures
-
- Step 2: Substitute the equilibrium concentrations into the expression
Kp = 9.1 x 10-6
-
- Step 3: Deduce the correct units of Kp
The units of Kp are Pa-1
Therefore, Kp = 9.1 x 10-6 Pa-1
- Some questions only give the number of moles of gases present and the total pressure
- The number of moles of each gas should be used to first calculate the mole fractions
- The mole fractions are then used to calculate the partial pressures
- The values of the partial pressures are then substituted in the equilibrium expression
Worked Example
Calculating Kp of hydrogen iodide equilibrium reaction
The equilibrium between hydrogen, iodine and hydrogen iodide, at 600 K, is as follows:
H2 (g) + I2 (g) ⇌ 2HI (g)
At equilibrium, the number of moles present are:
- H2 = 1.71 x 10-3
- I2 = 2.91 x 10-3
- HI = 1.65 x 10-2
The total pressure is 100 kPa. Calculate the value of Kp for this reaction.
Answer
-
- Step 1: Calculate the total number of moles
Total number of moles = 1.71 x 10-3 + 2.91 x 10-3 + 1.65 x 10-2
Total number of moles = 2.112 x 10-2
-
- Step 2: Calculate the mole fraction of each gas
-
- Step 3: Calculate the partial pressure of each gas
H2 = 0.0810 x 100 = 8.10 kPa
I2 = 0.1378 x 100 = 13.78 kPa
HI = 0.7813 x 100 = 78.13 kPa
-
- Step 4: Write the equilibrium constant in terms of partial pressure
-
- Step 5: Substitute the values into the equilibrium expression
Kp = 54.7
-
- Step 6: Deduce the correct units for Kp
All units cancel out
Therefore, Kp = 54.7
- Other questions related to equilibrium expressions may involve calculating quantities present at equilibrium given appropriate data